EP2751034B1 - Reduction of organic phosphorus acids - Google Patents

Reduction of organic phosphorus acids Download PDF

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Publication number
EP2751034B1
EP2751034B1 EP12766501.6A EP12766501A EP2751034B1 EP 2751034 B1 EP2751034 B1 EP 2751034B1 EP 12766501 A EP12766501 A EP 12766501A EP 2751034 B1 EP2751034 B1 EP 2751034B1
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Prior art keywords
organic phosphorus
water stream
acid
phosphorus
level
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EP12766501.6A
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German (de)
English (en)
French (fr)
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EP2751034A1 (en
Inventor
Michael Combs
Denis FALLON
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Acetate International LLC
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Acetate International LLC
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

Definitions

  • the present invention relates generally to the removal of organic phosphorus acids from effluent water streams, more particularly to remove organic phosphorus acids by using metal salts and adjusting the pH level of the water streams.
  • Phosphorus is a nutrient vital to human, animal, and plant life. It is one of the most common substances in our environment, naturally occurring in our food, water, and bodies, as well as, in human and animal waste. However, excess phosphorus in freshwater systems can lead to undesirable consequences. For example, an excess amount of phosphorus in bodies of water can lead to accelerated plant growth, algae blooms, low dissolved oxygen, and death of certain fish, invertebrates and other aquatic animals.
  • Inorganic phosphate and organic phosphorus acids can often be found in byproducts from manufacturing plants, animal production facilities, detergents, wastewater, and storm water. Effluent streams from such plants commonly contain inorganic phosphate and organic phosphorus acids, which may be discharged into rivers and lakes. Municipal wastewater may contain from 5 to 20 mg/l of total phosphorus, of which 1-5 mg/l is organic and the remaining in inorganic form. Realizing the undesirable effects of excess phosphorus in water, countries and municipalities have imposed limits on the amount of phosphorus that may be permitted in effluent streams.
  • Phosphorus may be removed from streams using filtration for particulate phosphorus, membrane technologies, precipitation, assimilation, or enhanced biological phosphorus removal methods.
  • inorganic phosphates may be removed by adding a coagulant and mixing the wastewater and coagulant mixture through the use of multivalent metal ions, such as calcium, aluminum and iron.
  • Organic phosphorus typically is removed by converting to inorganic phosphates and precipitating using conventional methods. Nonetheless, most phosphorus removal treatments mainly target the removal of inorganic phosphates, but do not target or optimize the removal of organophosphorus acids in the water stream. These water streams with organic phosphorus acids are released into rivers and lakes. Hence, potentially causing harm to the environment.
  • US 2008/0242913 A1 relates to the destruction of the chemical weapons and describes a method comprising oxidizing a hydrolysate of a chemical agent to produce an aqueous layer and an organic layer and removing the organophosphorus concentration from the aqueous layer by oxidation.
  • the present invention is directed to a process according to claims 1 to 4.
  • the present invention is directed to a process for reducing the level of organic phosphorus acids contained in an effluent water stream, e.g., an effluent waste water stream, in an economical manner.
  • the water stream may be derived from a manufacturing plant, residential waste, storm drainage, or elsewhere.
  • effluent stream or "effluent” refer to any water post treatment.
  • phosphorus acids refers to oxoacids of phosphorus.
  • Several non-limiting examples are provided in Table 1.
  • the phosphorus acid is selected from the group consisting of methyl phosphonic acid and dimethyl phosphinic acid.
  • the process of the present invention comprises adjusting the pH level of the effluent water stream comprising one or more organic phosphorus acids to reach an optimal pH level, a pH between 4 and 6, and adding a metal salt to the water stream.
  • the metal salts reacts with the organic phosphorus acid to form a precipitant, which may be subsequently separated from the water stream via filtration, decanting, or other means to yield a final water stream containing less organic phosphorus acids than the initial water stream.
  • Multivalent metal salts such as ferric chloride
  • ferric chloride are typically used to remove inorganic phosphate from waste water. It has now been surprisingly and unexpectedly discovered that at an optimal pH level between 4 and 6 ferric chloride, and in particular the cationic species thereof, effectively reacts with the organic phosphorus species to form a precipitant and thereby reducing the amount of organic phosphorus acids contained in the waste water the removal efficiency of which is impacted by the pH while inorganic phosphate is not impacted.
  • the present invention is to a process of reducing organic phosphorus acids, such as methyl phosphonic acid and dimethyl phosphinic acid, using ferric chloride and by adjusting the pH of the waste water to an optimal level.
  • the optimal pH level of the waste water may be adjusted by using the multivalent metal salt, a basic aqueous solution or an acidic aqueous solution.
  • a suitable metal for use in the multivalent metal salt is iron.
  • a suitable multivalent metal salt is ferric chloride.
  • suitable basic aqueous solution may be solutions of sodium hydroxide, potassium hydroxide, or other alkali metal solutions that have a pH greater than 7, e.g., greater than 8, greater than 9, or greater than 10.
  • suitable acidic aqueous solution include, for example, sulfuric acid, nitric acid, hydrochloric acid, sulfuric acid, or other strong acidic acid solutions having a pH of less than 6, e.g., less than 5, less than 4, or less than 3.
  • the acidic aqueous solution has a pH of from 1 to 6, e.g., from 1 to 5, from 1 to 4 or from 2 to 4.
  • the pH level of the water stream may initially range from between pH 5 to 8.
  • an acidic or a basic aqueous solution may be added to the waste water.
  • the optimal pH level is between pH 4 and pH 6. It has been discovered that at the optimal pH level, multivalent metal salt binds to organic phosphorus acids to form a metal phosphorus complex, which advantageously precipitates from the water stream, where removal efficiency decreases outside these optimal ranges.
  • the precipitants may be filtered or decanted using conventional solid particle separation techniques.
  • an excess amount of metal salt may be used to precipitate the organic phosphorus acids.
  • the molar ratio of metal salt to organic phosphorus acid may be greater than 1:1, e.g., greater than 2:1, greater than 3:1, greater than 4:1, or greater than 5:1. It has been found that in accordance with the present invention, the majority of the organic phosphorus acid in the water stream preferentially binds to the metal salt and may be subsequently removed from the water stream. In some embodiments, for example, at least 50% of the organic phosphorus acid may be removed, at least 65% may be removed, at least 80% may be removed, or at least 85% may be removed, or at least 90% may be removed from the water stream.
  • the effluent stream is substantially free of phosphorus acids, e.g., the effluent stream comprises less than 5 mg/l phosphorus acids, less than 4 mg/l phosphorus acids, or less than 3.2 mg/lphosphorus acids.
  • the process according to the present invention efficiently and economically removes phosphorus from waste water.
  • Acetic anhydride is made by reacting acetic acid in the presence of a phosphate catalyst under high temperature to form a ketene intermediate.
  • the ketene intermediate then reacts with acetic acid to form acetic anhydride.
  • organic phosphorus acid compounds such as methyl phosphonic acid and dimethyl phosphinic acid, are formed as byproducts, which may find their way into the waste water of the acetic anhydride production plant.
  • the inventive process may be used to facilitate removal of these compounds from the waste water stream.
  • Figure 1 illustrates an exemplary process or method 100 for removing organic phosphorus acids from waste water in an acetic anhydride manufacturing process, or other process or waste stream, in accordance with one embodiment of the present invention.
  • waste water from the acetic anhydride process is collected in an influent tank, which contains organic phosphorus byproduct.
  • the amount of organic phosphorus byproduct may be anticipated based on the acetic anhydride manufacturing process.
  • the pH may vary.
  • the pH level in the waste water may be measure.
  • the pH level in the waste water may be adjusted using acidic aqueous solution, such as sulfuric acid, or basic aqueous solution, such as sodium hydroxide or potassium hydroxide. The amount of acidic aqueous solution or basic aqueous solution that is added to the waste water is based on the measured pH.
  • ferric chloride is added to the waste water to react with the phosphorus acid and form a precipitant, which precipitates from the water stream.
  • organic phosphorus removal efficiency depend on the pH of the waste water while inorganic phosphorus is only slightly impacted or not impacted at all.
  • the inventors discover that at an optimal pH level between pH 4.0 and pH 6.0, the majority of the organic phosphorus acids reacts with the cation, e.g., iron, of the ferric chloride, and precipitates out of the waste water and may be effectively removed.
  • the inventors also discover that at high or low pH, inorganic phosphorus is effectively removed from the waste water stream.
  • organic phosphorus acid may be selectively and effectively removed at pH between 4.0 and 6.0 and inorganic phosphorus may be removed at pH outside of that range.
  • the amount of ferric chloride added may be determined by the anticipated amount of organic phosphorus contained in the water stream.
  • An excess amount of metal salt, e.g., ferric chloride, may be added to the waste water as indicated above.
  • the molar ratio of metal salt, e.g., ferric chloride, to organic phosphorus may be at least 1:1, at least 2:1, at least 3:1, at least 4:1, or at least 5:1.
  • the addition of ferric chloride to the waste water may shift the pH of the waste water outside of the optimal pH level, i.e., the waste water has a pH lower than pH 4.0, or pH 3.5, or pH 3.0.
  • basic solutions such as sodium hydroxide or potassium hydroxide, may be added to readjust the pH to the optimal level.
  • the iron phosphorus precipitant may be removed using various methods known in the art, including ultra filtration membrane, sand filter, decanting, or slow settling filter, and may be disposed.
  • a suitable amount of aqueous basic solution or acidic solution may be added to the residual liquid to achieve a neutral pH if the residual liquid is to be disposed of.
  • the residual liquid may be used for additional processes rather than disposed of, it may not be necessary to adjust the pH of the residual liquid.
  • the waste water with neutral pH and reduced phosphorus content may be released to river or other water source or sent to waste water treatment.
  • Figure 2 shows a graph of total organic phosphorus concentration versus pH level of an effluent water stream, e.g., waste water stream.
  • the total organic phosphorus level is high when the waste water has a pH 3 to pH 3.5.
  • the organic phosphorus level is significantly lower when the pH of the waste water is between about pH 4 and about pH 6.
  • the total organic phosphorus level in the waste water is also high when the pH for waste water is greater than about 6 or greater than about 7.
  • Figure 2 also compares the use of 2 and 3 moles of iron for each 1 mole of phosphorus.
  • the amount of organic phosphorus removed for 2:1 mol ratio for Fe:P is similar to the amount of organic phosphorus removed for 3:1 mol ratio of Fe:P.
  • the use of 3:1 mol ratio of Fe:P did not appear to provide an advantage over 2:1 mol ratio of Fe:P. Nonetheless, the difference between 2:1 mol ratio and 3:1 mol ratio is significant because by using 3:1 mol ratio of Fe:P the total organic phosphorus acid in the water stream is reduced from 6.8 mg/L to 4.9 mg/L. This 28% increase in total organic phosphorus acid removal brings the total organic phosphorus acid amount to below 5/0 mg/L.
  • Figure 3 shows a graph of methyl phosphonic acid concentration versus pH level of the water stream. Similar to Figure 2 , when the pH level of the waste water is outside of the optimal range of about pH 4 and pH 6, a high level of methyl phosphonic acid was detected in the waste water. Surprisingly and unexpectedly, between pH 4 and pH 6, a very low level of methyl phosphonic acid was detected, less than 2.7 mg/l. Significantly, at pH 5.0 using 3:1 mole ratio of Fe:P, the amount of methyl phosphonic acid is reduced to 0.8 mg/L.
  • Figure 3 also shows that the use of 3:1 mol ratio of Fe:P provides a significant advantage over 2:1 mol ratio of Fe:P.
  • the amount methyl phosphonic acid in the water stream was reduced from 2.1 mg/L to 0.8 m/L, which is a 62% increase in methyl phosphonic acid removal.
  • the amount of methyl phosphonic acid at different pH levels and the effect of Fe:P molar ratio are shown in Table 2.
  • Figure 4 is yet another example of the effect of pH level on phosphorus acid.
  • Figure 4 shows a graph of dimethyl phosphinic acid concentration versus pH level of the water stream.
  • the amount of dimethyl phosphinic acid in the water stream is about 6.6 mg/L.
  • the amount of dimethyl phosphinic acid decreases.
  • the amount of dimethyl phosphinic acid is lowest for 2:1 mole ratio of Fe:P at pH 6.1 and for 3:1 mole ratio of Fe:P at pH 4.0. This demonstrates that both pH and mole ratio of Fe:P effects the amount of dimethyl phosphinic acid removal.
  • the level of dimethyl phosphinic acid is lowest at about pH 4.0.
  • the concentration of dimethyl phosphinic acid again shows a minimum at pH between 4 and 6.
  • the amount of dimethyl phosphinic acid at different pH levels and the effect of Fe:P molar ratio are shown in Table 3.
  • the graphs shown in Figures 2 to 4 indicate that adjusting the pH level of water stream to an optimal level, e.g., less than 7.0, preferably between about pH 4.0 to about pH 6.0, beneficially increases the removal of organic phosphorus acid. Therefore, a pattern can be established that a maximum amount of organic phosphorus acid may be removed at between about pH 4.0 to pH 6.0.
  • the data also indicates that the use of 3:1 mol ratio of Fe:P beneficially removes more organic phosphorus acid over 2:1 mol ratio of Fe:P.
  • Figure 5 shows a graph of the effect of temperature and pH level on the concentration of total organic phosphorus acid in the water stream using 3:1 mole ratio of Fe:P. As shown, at about pH 3, the level of total organic phosphorus acid is the highest in the water stream for all three temperatures. For all three temperatures, as the pH of the water stream increases, the level of total organic phosphorus acid in the water stream decreases.
  • the amount of total organic phosphorus acid reaches their respective lowest level at about pH 5 at 25°C and 35°C and at about pH 6 for 15°C.
  • temperature appears to have an effect with the removal of total organic phosphorus acid.
  • the amount of total organic phosphorus acid in the water stream is 12.9 mg/L.
  • the amount of total organic phosphorus acid in the water stream decreases to 6.2 and 6.9, respectively.
  • the temperature effect does not appear to influence the amount of organic phosphorus acid in the water stream at pH greater than 4.0.
  • the amount of organic phosphorus acid in the water stream is higher at 15°C than at ambient temperature or at elevated temperature (35°C).
  • the amount of organic phosphorus acid in water for all three temperatures at pH 5 only differs by 0.3 mg/L.
  • the amount of total organic phosphorus acid at different temperature is shown in Table 4.
  • Table 5 is a comparison of the effect of pH on the total organic phosphorus acid versus inorganic phosphorus removal. As shown, the initial inorganic phosphorus in the water stream is 69.7 mg/L. Regardless of the molar ratio of Fe:P or the pH of the water stream, over 99.6% of the inorganic phosphorus is removed from the water stream. In comparison, as discovered by the inventors, the amount of total organic phosphorus acid removed is pH dependent. At a pH between 4.0 and 6.0, over 80% of organic phosphorus acid is removed. However, at pH levels outside of this range, no greater than 68% of the organic phosphorus acid is removed from the water stream.
  • a 10 g sample containing 17 mg/L methyl phosphonic acid was obtained.
  • the pH of the sample is measured at pH 7.0.
  • a 0.02g of 37% ferric chloride solution was added to the methyl phosphonic acid solution.
  • the pH of the mixture was measured to be approximately 3.0.
  • 0.1M NaOH is added to raise the pH of the solution to 4.0.
  • the solution was agitated for less than 60 seconds.
  • the temperature was maintained at room temperature (approximately 25 °C.
  • the precipitate was filtered using a 0.45 ⁇ m PTFE filter.
  • the experiment was repeated at different pH, temperature, and Fe:P molar ratio.
  • the total amount of phosphorus was measured using an inductively coupled plasma before the experiment.
  • the amount of inorganic phosphorus was measured using a spectrometric wet chemical test.
  • the amount of organic phosphorus acid was calculated by subtracting the amount of inorganic phosphorus from the total amount of phosphorus measured and reported in the above tables.
  • the amount of methylphosphonic acid and dimethyl phosphinic acid were measured using ion chromatography with suppressed conductivity method.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Sludge (AREA)
EP12766501.6A 2011-09-01 2012-08-31 Reduction of organic phosphorus acids Active EP2751034B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/223,736 US9346692B2 (en) 2011-09-01 2011-09-01 Reduction of organic phosphorus acids
PCT/US2012/053381 WO2013033557A1 (en) 2011-09-01 2012-08-31 Reduction of organic phosphorus acids

Related Child Applications (1)

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EP19204588.8 Division-Into 2019-10-22

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EP2751034B1 true EP2751034B1 (en) 2020-05-20

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US (1) US9346692B2 (ja)
EP (1) EP2751034B1 (ja)
JP (2) JP6374790B2 (ja)
KR (1) KR20140059835A (ja)
CN (1) CN103842301B (ja)
MX (1) MX2014002448A (ja)
WO (1) WO2013033557A1 (ja)

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MX2018008884A (es) 2016-01-20 2019-02-21 Daicel Corp Metodo para producir derivados del ceteno.
US10717662B2 (en) * 2018-02-07 2020-07-21 Honeywell International Inc. Process for the removal of iron and phosphate ions from a chlorinated hydrocarbon waste stream
CN108609788A (zh) * 2018-04-23 2018-10-02 浙江奇彩环境科技股份有限公司 一种磷系阻燃剂废水的处理工艺
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CN113264619A (zh) * 2021-03-01 2021-08-17 深圳市盘古环保科技有限公司 一种垃圾渗滤液膜浓缩液中有机磷酸酯的处理方法

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KR20140059835A (ko) 2014-05-16
US9346692B2 (en) 2016-05-24
MX2014002448A (es) 2014-04-10
EP2751034A1 (en) 2014-07-09
CN103842301A (zh) 2014-06-04
JP6805208B2 (ja) 2020-12-23
WO2013033557A1 (en) 2013-03-07
CN103842301B (zh) 2018-04-06
JP2018183779A (ja) 2018-11-22
JP6374790B2 (ja) 2018-08-15
JP2014527905A (ja) 2014-10-23
US20130056422A1 (en) 2013-03-07

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